Wetting, dispersing, or emulsifying agent



Patented Jan. 14, 1941 rro STATES 2,228,986 WETTING, DISPERSING, OREMULSIFYING AGENT Delaware No Drawing. Application February 23, 1938,Serial No. 191,964

12 Claims. (Cl. 252-356) This invention relates to new products adaptedfor use as wetting, dispersing or emulsifying agents. It relates moreparticularly to new products including in admixture tertiary alkylol- 5amines'having more than one alcoholic hydroxyl group partiallyesterified by higher fatty acids and polyhydric alcohols partiallyesterified by higherfatty acids: and it includes not only these newproducts, but also a new process for their 10 production. The newproducts of the invention are stable, are highly effective inacid-solution, and show a marked resistance to alkalies.

The new compositions of the present invention contain the twocharacteristic components in 15 more or less widely varying proportions,and may contain other constituents. They are characterized by theircontent of a substantialproportion of an alkylolamine, partiallyesterified' by a higher fatty acid, represented by the formula Rr-N inwhich R1, R2 and R3 arealkyl groups or sub- 20 stituted alkyl groups,which may be the same or different, at least one of which has at leastone R4COO substituent, (R4 representing the long carbon-linked chain ofa higher fatty acid) and at least one of which has at least one H(alcoholic hydroxyl) substituent, compounds having an R4000 substituentand an OHsubstituent in the same substituted alkyl group, with the otheralkyl groups substituted or unsubstituted, being included, together witha substantial proportion of a p'olyhydric alcohol partially esterifiedby a higher fatty acid.

The newcompositions may be prepared in various ways. One advantageousmethod of preparing them involves the simultaneous alco- 40 holysis orre-esterification of such esters of higher fatty acids as the naturalfats or oils (triglycerides) or di-esters of ethylene glycol or the likewith tertiary alkylolamines having more than one alcoholic hydroxyl anda polyhydric al- -i5coho1, in proportions such that after thealcoholysis-or re-esterification, there will be in the reaction asubstantial proportion of partially es'- terified alkylolamine having atleast one free alcoholic hydroxyl group in the' amine nucleus and asubstantial proportion of partially esterifled polyhydric alcohol, whichlatter may include mono and diglycerides' as well as the productsresulting from the partial esterification of the polyhydric alcohol usedin the reaction, such 55 as'glycerin, ethylene glycol, polyglycols orpolyglycerols, etc. In this specification and the appended claims, theterm amine nucleus is used to designate that portion of the molecule ofthe amine ester which is linked through a carbon atom or carbon atoms toone or more RCOO 5 groups; the term higher fatty acid is used todesignate those carboxylic acids, generally having at least twelvecarbon atoms, which occur in natural oils, fats and waxes, ormodifications I thereof such as occur in blown or bodied oils; and theterm polyhydric alcohol is used to designate those alcohols having morethan one hydroxyl group, including glycerin, ethylene glycol,diethyleneglycol, propyleneglycol, polyglycerols, polyglycol ethers,glycol-glycerol ethers, polyglycerol-glycol ethers, polyglycol glycerolethers, other polyalkylene ethers having a plurality of hydroxy groups,etc.

' In general, such alcoholysis or re-esterification is readily carriedout by heating the fatty acid ester, the tertiary alkylolamine and thepolyhydric alcohol to temperaturesjn excess of -100 C., but below thetemperature at which decomposition takes place. No added catalyst isrequired. Advantageously, temperatures ranging from 150 to 180 C. areused. In the reaction which takes place, no water is formed,

and no water is available for thehydrolysis of such catalysts asphosphates, hydroxides, or

other similar alkalies.

The new products may also be readily produced by the admixture ofasuitable partially esterified polyhydric alcohol, such as one or more40 of those referred to above, with an ester or esters of a tertiaryalkylolamine having one or more free hydroxyl groups in the aminenucleus, produced, for example, as described in our copendingapplication Serial No. 180,993, filed December 21, 1937, by thealcoholysis of a fatty acid ester with a tertiary alkylolamine, the tworeactants being used in proper proportions as described in saidapplication. Admixtures so produced will be free from the simple saltsor soaps of the fatty acid; and the amine; The partially esterifledpolyhydric alcohol may be produced by any of the known methods forproducing the so-cal1ed super-glycerinated fats, mono or diglycerides,etc.

Other methods may be used for producing the new compositions,althoug'h'in some cases the products produced will not have all theadvan-- tages of the products produced by the processes outlined above.For example, a suitable fatty acid may be condensed with a tertiaryalkylolamine at relatively high temperatures, with the production of aproduct containing a substantial proportion of the ester or esters ofthe fatty acid and the tertiary alkylolamine admixed 10 with the salt orsoap of the alkylolamine with the fatty acid; and the resulting productmay then be admixed with a suitable proportion of a partially esterifledpolyhydric alcohol. This method is satisfactory if the presence of thesimple salt 38 or soap of the fatty acid and the alkylolamine in thefinal product is unobjectionable; but it should be avoided if a productis desired having a very high stability in the presence of acids, as thesimple salts or soaps tend to decompose in 80 such solution.

When the new process outlined above, involving the simultaneousalcoholysis or re-esterification of a fatty acid ester with a tertiaryalkylolamine and a polyhydric alcohol is used, the par- 85 tiallyesterified alkylolamine in the resulting a reaction product obtained bysubjecting the alkylolamine, the fatty acid ester and thepolyhydricalcoholto. high temperatures, but instead of using acetic acidfor the neutralization of the reaction product, other organic acids,such as opropionic acid, butyrlc acid, lactic acid, citric acid, or thelike may be used, or inorganic acids, such as hydrochloric acid, nitricacid, sulfuric acid, phosphoric acid, or other inorganic acids may beused. To produce products'ior special 45 functions, higher fatty acids,such as those derived from any of the common vegetable or animal oilsmay be used to neutralize the product, with the production of the higherfatty acid salts or soaps of the esterifled amines. It must also beunderstood that the new' compositions, instead of being used inneutralized form, may be used in unneutralized form, advantageously inacid solution, in which they are quite stable and readily disperse. Inthe specification and the appended claims, the term ester of a. tertiaryalkylolamine -is used to designate not only the esters in the form offree bases, but also their salts or neutralized products.

Even where the compositions are produced by the admixture of a partiallyesterifled polyhydric alcohol with theproduct resulting from heating afree fatty acid and a tertiary alkylolamlne'to high temperatures, itwill be found advantageous to neutralize the product. when a free fattyacid and a tertiary alkylolamine are heated together to hightemperatures, the reaction involved is quite complex, but apparently itinvolves an initial reaction between the amine and the, fatty acid toform a simple soap or salt, a portion of which is subsequentlyrearranged and condensed at the high temperatures to form the ester'ofthe free base, with elimination of water, so that the resulting productcontains a mixture of the simple saltor soap of the amine and the fattyacid and esters of the amine and the fatty acid.

Such a product will necessarily be partly in the form of the free base,unless the fatty acid has been used in such large proportions as tocompletely esterify and neutralize the amine, and

such portion of the product as is in the form of the free base isadvantageously neutralized when used in the new compositions of thepresent invention.

Among the tertiary amines which may be used in the production of the newproducts of the present invention are a wide range of tertiary alkyloland tertiary alkylamines. It is understood that the terms alkylol andalkyl are used conventionally in chemistry to refer to the long chainparaflin compounds which are noncyclic and aliphatic in nature. We havefound, however, that the alicyclic-hydroxyalicyclic, thehydroxy-alicyclic, and the alkyl hydroxy-alicyclic amines are, "withrespect to their reaction with esters of higher fattyacids, and withrespect to the nature of the products produced by such reaction, similarto the corresponding alkyl and alkylol radicals present. For thisreason, for the purpose of describing thepresen't invention only, it isunderstood that theterms' "alkyl and alkylol include within their scope,alicyclic and hydroxy-alicyclic groups. The two essentials are that thealkylolamine contain at least two alcoholic hydroxyl groups, which maybe attached to the same or diiferent carbon chains, and be a tertiaryamine, that is, with three alkyl or alkylol groups linked through acarbon atom to the nitrogen atom. Included among the suitable amines aretriethanolamine, diethanolalkylamines, such as diethanolethylamine,diethanolpropylamine, etc., tertiary glyceryl amines, such astri-dihydroxypropylamine, dihydroxypropyldialkyl-amines, such asdihydroxypropyldiethylamine, didihydroxypropylalkylamines,diethanolmethylamine, tripropanolamine, dipropanolmethyl'amine,cyclohexanoldiethanolamine, di-cyclohexanolethylamine, etc. All suchproducts may be readily prepared by known processes, and all of them aretertiary amines having at least two alcoholic hydroxyl groups, thusbeing adapted to form esters with higher .fatty acids, such estersh'aving at least one free hydroxyl group. Typical of the amineswhichmay' be used are the following:

(021140 E) 3N 'lriethanolamine (02m) Diethanolethylamine canon emote-N Ca Diethanoimethylamine 3H5( )2]3N Tri-dihydroxypropylamine(triglycerylamine) [0311mm] [QaHK MP-N Di-dihydroxyp'ropylethylamine(diglycerylethylamine) [Ca t( )2] a m-N Dih droxypropyldiethylamineglyceryl diethylamine) (CaHlOHhN Tripropanolamine 2 5) Dipropanolethylamine 2 5) Di-phenylnropanolethyiamine (C 2H4O H)N (CsHioO H) Gyclohexanoldiethanolamine iHmO H) 2 5)Dicyclohexanolethylamine ness; but such esters as the distearicor'dioleic acid-esters of ethylene glycol, etc., may be used.

' The triglycerides whichmay be used include such vegetable oils ascocoanut and palm kernel drying and semidrying'oils such as corn oil,rape seed oil, soya bean oil, sun-flower seed oil, linseed oil, perillaoil, etc.,' .as well as the animal and marine oils, such astallow,xsardine oil, menhaden oil, etc. Blown or bodied oils, such asblown ca's"-.

oil, olive oil, castor oil, palm oil, peanut oil, the

" emulsifying properties in the presence of acids,

and their marked resistance to alkalies. We believe that the stabilityand foaming, wetting and emulsifying propertiesin the presence of acidsfollows fromthe fact that the surface-active ion of the amine portion ofthe new-compositions is the cation; and where the compositions areintended for use in acid solution, it is a decided advantage to preparethem in such a way as to prevent the presence of simple salts or soapsof the amine and the higher fatty acids in the prodnot. We believe theresistance oi the new compositions to alkalies is due to the inclusionof the original oils from which they were derived. Castor oil and blowncastor oil produce products having somewhat special characteristics, asdue to the presence of oxygen in the long hydrocarbon chaincharacteristic of the fatty acids, the-alkylolamine esters havingdecreased solubility in hydrocarbon oils, and increased solubility inaqueous media. Thus the-mono-rlcinoleic acid ester of triethanolamine,for example, isquiteinsoluble in hydrocarbon oils, but dissolves indilute acid solutions, orforms salts,for example,

with acetic acid, which yield clear solutions in water. Products derivedfrom cocoanut and palm kernel oils, which are characterized by havingfatty acids with relatively short hydrocarbon uchains, such as lauricacid, for example, the mono-acid ester of'triethanolamine derivedfromtriethanolaniine and cocoanut oil, have outstanding advantages foruse with hard water containing calcium or magnesium salts, as they donot readily form insoluble precipitates in suchhard waters.

.or magnesium salts.

' tertiary alkylolamine, an ester of a higher fatty acid, and apolyhydric alcohol, such as glycol or glycerin, the proportions of thefatty acid ester, the alkylolamine, and the polyhydric alcohol should besuch that the fatty acid ester is equivalent to, from the fatty acidstandpoint, or can esterify, by alcoholysis or re-esterification, but aportion of the alcoholic hydroxyl groups of the amine anda portion ofthe alcoholic hydroxyl groups of the polyhydric alcohol, including thatcombined in the original fatty acid ester used, so that the finalproduct obtained is a mixture of partially esterified amine, having atleast one alcoholic hydroxyl'in the amine nucleus, and partiallyesterified polyhydric alcohol, containing at least one alcoholichydroxyl in'the partially esterified polyhydric alcohol. Substantiallythe same product may be prepared by the reaction of a partiallyesterified polyhydric alcohol, such as a mono or diglyceride, with atertiary alkylolamine, using an excess of the partially esterifiedpolyhydric alcohol, and permitting the alcoholys'is or re-esteriilcationto go only partially to completeness, so that the product obtained is amixture of partially esterified alkylolamine and initial partiallyesterified polyhydric alcohol, and undoubtedly includes a substantialamount of free polyhydric alcohol, which may be removed by washing orthe like if desired.

.I'he invention will be illustrated by the following speciflc examples,but it is not limited thereto.

- Example 1.Commercia1 triethanolamine, cocoanut'oil and glycerin theproportions of 1 mole of cocoanut oil to 3 moles of triethanolamine andat least 1 mole of glycerin are heated to atemperature of between aboutand C. for a period of about 2 hours. The resulting product containssubstantial amounts of the mono-fatty 'acidester of triethanolamine andthe mono and til-fatty acid esters of glycerin, with minor proportionsof the initial cocoanut oil, glycerin, and unreacted triethanolamine.The amine portion of the reaction product is advantageously convertedinto the acetate, by the addition of 3 moles of glacial acetic acid,forming a salt which is readily dispersible in water. 01 course, insteadof using acetic acid for neutralizing the product, other'acids. such asthose referred to above, may be used.- Theproduct has extremely goodwettingf emulsifying and: detergent properties.- is highly eflective .inacid solution, is highly resistant, to alkalies, and is very useful inhard watar, as it is not readily precipitated by calcium '-Ezample2.'Irig lyceryla mine (tn-mysterypropylamlne) and castor oil are reactedin the proportions of 3 moles of castor oil to 2 moles oftriglycerylamine, with the production of a product consistingpredominantly of the di-ricinoleic acid ester of the triglycerylamine.To this product is added a substantial proportiomfor example, about 50%,of the mono-ricinoleic acid ester of glycerin. Advantageouslythe'triglycerylamine ester is neutralized, as by the addition of 2 molesof a suitable acid, such as acetic acid, before the addition of themono-glyceride. The product has excellent wetting, emulsifying anddetergent properties.

Example 3.Palm kernel oil and diethanolethylamine, in the molecularproportions of 3 moles of the amine to 1 mole of the oil, are heatedtogether with 1 mole of a polyglycerol to a temperature between about150 and 180 C. for about 2 hours, with the production of a reactionproduct containing substantial amounts of the mono-ester of thediethanolethylamine and of super-glycerinated oil.

Example 4.Commercial triethanolamine and a fatty oil, in the molecularproportions of 3 moles of the amine to 1 mole of the oil are heatedtogether with 1 mole of ethylene glycol to a temperature between about150 and 180 C. for about 2 hours, with the production of a reactionproduct containing substantial amounts of the monoester of thetriethanolamine together with substantial amounts of partiallyesterified glycerin and ethylene glycol.

Example 5.The mono-ricinoleic acid ester of glycerin andtriglycerylamine are heated together to temperatures between about 150and 180 C. for about 2 hours in the proportions of 2 moles of themono-'ricinolein to 1 mole of the triethanolamine, with the productionof a product containing substantial amounts of mono-ricinolein, themono-ricinoleic acid ester of triethanolamine, and glycerin. If, insteadof mono-ricinolein, diricinolein be used in somewhat lesser proportions,a corresponding product is obtained containing substantial amounts ofunchanged di-ricinolein, together with a minor, and in generalinsignificant, amount of mono-ricinolein.

It has been heretofore pointed out that for the purpose of describingthe present invention, the terms alkyl and alkylol are to be construedas including alicyclic and hydroxyalicyclic groups which behave in amanner similar to the alkyl and alkylol groups with respect to reactionsin-' volved in the ,present invention. It is to be understood thataralkyl and hydroxyaralkyl groups are I similarly included providedtheir linkage to the nitrogen atom is through a side chain carbon andprovided, in the case of the hydroxyaralkyl groups, the hydroxy group isattached to a side chain carbon. Aralkyl or hydroxyamines, which may beused in the production of the new products of the present invention maybe produced, for example, by reaction between such compounds as thechlorethanolamines and aromatic compounds such as benzene ornaphthalene, with'replacement of the halogen by the aryl group and theproduction of aralkyl or hydroxyaralkylamines, such as monophenyl ordiphenyltriethanolamine or mononaphthyl or dinaphthyltriethanolamine.

We claim:

l. Compositions, an essential constituent of which is a mixture of ahigher fatty acid ester of a tertiary alkylolamine, said ester having atleast one alcoholic hydroxyl group in the amine nucleus, and apolyhydric alcohol partially esterified by a higher fatty acid, saidpartially esterified polyhydric alcohol having at .least one freealcoholic hydroxyl group.

2. Compositions. an essential constituent of which is a mixture of acompound of the class consisting of monoand dihigher fatty acid estersof triethanolamine and a polyhydric alcohol partially esterified withhigher fatty acids.

3. Compositions, an essential constituent of which is a mixture of ahigher fatty acid ester of a tertiary alkylolamine, said ester having atleast one alcoholic hydroxyl group in the amine nucleus and a higherfatty acid ester of glycerin having at least one of the hydroxyl groupsof the glycerin molecule free. i

4. A composition, an essential constituent of which is a mixture of asuper-glycerinated fat and a higher fatty acid ester of a tertiaryalkylolamine having at least one alcoholic hydroxyl group in the aminenucleus.

5. Compositions as in claim 1, which are substantially free from saltsof the tertiary alkylolamine with higher fatty acids.

6. Compositions, an essential constituent of which is a mixture of acompound of the formula in which R1, R2 and R3 are alkyl groups at leastone of which is substituted by an RACOQ group, in which R4 representsthe long carbon-linked chain characteristic of a higher fatty acid, andat least one of which is substituted by an-OH group, and a compound ofthe formula R4COCX in which R4 represents the long-carbon linked chaincharacteristic of a higher fatty acid and X represents a polyhydricalcohol residue having at least one free OH group.

,7. The process of producing compositions adapted for use as wetting,emulsifying and detergent agents, which comprises heating an. ester of ahigher fatty acid with a tertiary alkylolamine having more than onealcoholic hydroxyl group and a polyhydric alcohol in proportions suchthat, after the resulting alcoholysis or re-esterification, there is atleast one free alcoholic hydroxyl group in the amine nucleus of theamine portion of the reaction product and a substantial proportion of apartially esterified polyhydric alcohol in the resulting product.

8. The process of producing compositions adapted for use as wetting,emulsifying and detergent agents, which comprises heating in excess of100 C. an ester of a higher fatty acid with a tertiary alkylolaminehaving more than one alcoholic hydroxyl group and a polyhydric.alcohohol in proportions such that, after the resulting alcoholysis orre-esterification, there is at least one free alcoholic hydroxyl groupin the amine nucleus of the amine portion of the reaction product and asubstantial proportionof a partially esterified polyhydric alcohol inthe re sulting product.

9. The process of producing compositions adapted for use as wetting,emulsifying and detergent agents; which comprises heating a' naturallyoccurring triglyceride with glycerin and a tertiary alkylolamine havingmore than one alcoholic group in proportions such'that, after theresulting reaction, there is at least one free alcoholic hydroxyl groupin the amine nucleus of the amine portion of the reaction product and asubstantial proportion of partially esterified glycerin in the resultingproduct.

10. The method of producing partially esteri- 7 fied polyhydric alcoholswhich comprises heating glycerides of higher fatty acids which comprisesheating glycerin and a triglyceride in the presence of an alkylolamine.

12. The method of producing monoand diglycerides of higher fatty acidswhich comprises heating glycerin and a triglyceride in the presence oftriethanolamine. I 4 I MELVIN DE GROOTE.

BERNHARD KEISER. CHARLES M. BLAIR, J R.

